From Amino Acids to Dihydrofurans: Functionalized Allenes in Modern Organic Synthesis
From Amino Acids to Dihydrofurans: Functionalized Allenes in Modern Organic Synthesis
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DOI：
10.1002/chin.200249224
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发表时间：
2002-09
期刊：
影响因子：
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通讯作者：
N. Krause;A. Hoffmann-Roeder;J. Canisius
中科院分区：
文献类型：
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作者：
N. Krause;A. Hoffmann-Roeder;J. Canisius
在这篇论文中，总结了目标定向合成涉及联烯的最新成果。通过氰基-吉尔曼试剂t-Bu2Cui-LiCN与2-氨基取代的烯醇酸酯8的1，6-加成反应，合成了可能成为维生素B6脱羧酶抑制剂的二烯α-氨基酸衍生物9，实现了氨基或酯基的选择性脱保护。2，5-二氢呋喃18是由相应的α-羟基烯通过环合反应得到的；为此，开发了新的方法(氯化氢气体或酸性离子交换树脂处理；金(III)-氯化物催化)。2-羟基-3，4-二烯酸酯14是由3，4-二烯酸酯12与二甲基二氧环己烷非对映选择性氧化生成的钛烯醇酸盐，而羟基烯丙烯16是通过铜催化的S N‘-取代炔丙基环氧化物15得到的。
In this account, recent accomplishments in the field of target-oriented synthesis involving allenes are summarized. Allenic α-amino acid derivatives 9, which are of interest as possible vitamin B 6 decarboxylase inhibitors, were prepared by 1,6-addition of the cyano-Gilman reagent t-Bu 2 CuLi-LiCN to 2-amino-substituted enynoates 8. and selective deprotection at either the amino or the ester group was realized. 2,5-Dihydrofurans 18 were obtained by cyclization of the corresponding α-hydroxyallenes; for this step, new methods (treatment with hydrogen chloride gas or acidic ion exchange resin; gold(III)-chloride catalysis) were developed. The 2-hydroxy-3,4-dienoates 14 were obtained by diastereoselective oxidation of titanium enolates formed from 3,4-dienoates 12 with dimethyl dioxirane (DMDO), whereas hydroxyallenes 16 were prepared by copper-mediated S N 2'-substitution of propargylic epoxides 15.